N(carbamyl(thiocarbamyl)methyl)phosphorodithio(thio) or phosphonodithio (thio)acetamides



United States Patent Office 3,420,918 Patented Jan. 7, 1969 3,420,918 N[CARBAMYL(THIOCARBAMYL)METHYL]PHOS- PHORODITHIO(THIO) R PHOSPHONODITHIO (THIO)ACETAMIDES Llewellyn W. Fancher, Lafayette, and David J. Broadbent,

San Jose, Calif., assignors to Staulfer Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 21, 1965, Ser. No. 500,193 US. Cl. 260-938 6 Claims Int. Cl. C07f 9/40 ABSTRACT OF THE DISCLOSURE Compounds of the formula wherein X and Y are oxygen or sulfur; R is lower alkyl, lower alkenyl, lower alkynyl, naphthyl, phenyl, substituted phenyl, wherein said substituents are halogen, lower alkoxy, lower alkyl or nitro; bornyl, isobornyl, cyclohexyl, lower alkoxya-lkyl, N-phthalimidomethyl or S-substituted-thioethyl wherein said substituents are lower alkyl, phenyl, naphthyl, halophenyl or alkyl phenyl; R and R are hydrogen, lower alkyl, phenyl, lower alkenyl or lower alkynyl; R is lower alkyl and R is lower alkoxy or lower alkyl. The compounds are useful as insecticides and acaricides.

This invention relates to certain new and novel organic compounds which may be used as elfective pesticides. More specifically, this invention relates to certain substituted canbamate acetamide phosphates and phosphonates and to the use of said compounds in effective insecticidal and acaricidal compositions.

The compounds comprising the instant class correspond to the general formula Y OR wherein X and Y are selected from the group consisting of oxygen and sulfur; R is a member selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, naphthyl, phenyl, substituted phenyl, wherein said substituents are selected from the group consisting of halogen, lower alkoxy, nitro, lower alkyl; bornyl, isobornyl, cyclohexyl, lower alkoxy-alkyl, N-phthalimidomethyl and S-substituted-thioethyl wherein said substituents are selected from the group consisting of lower alkyl, phenyl, naphthyl, halophenyl and alkyl pheny-l; R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl, lower alkenyl and lower alkynyl; R is lower alkyl, and R is lower alkoxy or lower alkyl. By lower alkyl and lower alkoxy we mean those members of said groups containing from 1 to carbon atoms, inclusive; by lower alkenyl and lower alkynyl we mean those members of said groups containing double and triple bonds, respectively, and containing from 2 to 10 carbon atoms, inclusive. Also included herein is a method of preparing, using and applying said compositions.

The compounds herein contemplated can be prepared by several methods. One such general method applied in preparing the compound-s was the condensation reaction between the appropriate substituted carbonylmethyl chloroacetamide and the requisite ammonium or alkali metal dialkyl phosphoro or phosphoro thioate or dithioate. The free phosphoric or phosphonic acid may be used also. The intermediate substituted carba moylmethyl chloroacetamide may be prepared from the appropriate carbamic acid ester or thioester and the appropriate 2chloro-N- (hydroxymethyl)acetamide, either unsubstituted or further N-substituted with R defined supra. The reaction proceeds readily in the liquid phase. The employment of an inert organic solvent is also useful, facilitating processing as well as agitation of the reactants. Solvents such as benzene, toluene, acetone, methylethyl ketone and the like may be employed. When the free phosphorus-containing acid is used the presenceof, a hydrogen halide acceptor such as sodium carbonate, triethylamine, pyridine, picoline and the like may be used as a catalyst. The reactions may be carried out at temperatures that permit operation in the liquid phase and which are between room temperature and reflux temperature of the solvent, if one is employed. Preferably the reaction mixture is refluxed, usually at an elevated temperature.

It has been found that the compounds of the present invention are particularly effective as insecticides and acaricides.

The compounds of the present invention may be made in accordance with the following examples.

EXAMPLE 1 Preparation of N-[ethoxycarbamyhnethyl]-0,0-diethylphosphorodithioyl acetamide To 11.7 g. (0.06 M) of ethoxycarbamoylmethyl chloroacetami'de (previously prepared from the ethyl ester of carbamic acid and Zwhloro-N-(hydroxymethyl) acetatnide) and 16.2 g. (0.08 M) of ammonium-0,0-diethylphosphorodithioate was added cc. of acetone. The mixture was stirred and refluxed for two hours. The precipitated ammonium chloride was filtered off and the acetone removed from the organic portion on a steam-bath with an air-jet. The residual organic liquid was dissolved in benzene, washed twice with water, dried over anhydrous magnesium sulfate, filtered, and the solvent evaporated. There was obtained 18.6 g. percent of theory) of light yellow viscous liquid, n P=1.5218.

Analysis for the title compound-Calculated: N, 8.13; S, 18.60; P, 9.01. Found: N, 7.90; S, 19.08; P, 9.48.

EXAMPLE 2 Preparation of N-[phenoxy-N-methylcarbamyhnethyl]- 0,0-diethylphosphorodithioyl acetamide By an analogous procedure to Example 1, 12.9 g. (0.05 M) of phenyl-N-methylcarbamyl chloroacetamide (previously prepared from phenyl-N-methylcarbamate and 2-chloro-N-(hydroxymethyl) acetamide), 14.2. g. (0.07 M) of ammonium-0,0-diethylphosphorodithioate in 75 ml. of acetone, gave after reflux and work-up 20.3 g. percent of theory) of a viscous liquid product, n =1.5485.

Analysis for the title compound-Calculated: N, 6.90; S, 15:80; P, 7.60. Found: N, 6.13; S, 14.64; P, 7.27.

EXAMPLE 3 Preparation of N-[ethoxy-N'-methylcarbamylmethyl]-N- allyl-0,0-diethylphosphorodithioyl acetamide To 12.4 g. (0.05 M) of ethoxy-N-methylcarbamylmethyl-N -allyl chloroacetamide (previously prepared from ethyl-N-methylcarbamate and 2-chloro-N-(hydroxymethyl)-N-(allyl) acetamide) in 75 ml. of benzene was added a neutral solution of aqueous potassium diethyldithiophosphate (0.08 M). The potassium diethyldithiophosphate was prepared from 14.9 g. (0.08 M) of diethyldithiophosphoric acid, 5.3 g. (0.08 M) of 85 percent potassium hydroxide and 25 ml. of water. The reaction mixture was stirred and refluxed for two hours and then cooled. The bottom aqueous layer was removed and the EXAMPLE 4 Preparation of N-[p-chlorophenylthioethoxy-N-methylcarbarnylmethyl]-0,0-dirnethylphosphorodithioyl acetamide To a mixture of 14 g. (0.04 M) of p-chlorophenylthioethyl-N-methylcarbamylmethyl chloroacetamide (previously prepared from p-chlorophenylthioethyl-N-methylcarbamate and 2-chloro-N-(hydroxymethyl)acetamide) and 75 ml. of methylethyl ketone was added with stirring 12.6 g. (0.08 M) of 0,0-dimethyldithiophosphoric acid and 8.1 g. (0.08 M) of triethylarnine. The reaction mixture mixture was stirred and refluxed for one hour and then cooled to C. It was washed with three 75 ml. portions of saturated aqueous sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent removed. There was obtained 18.5 g. (98 percent of theory) of the title compound, n 1.5629.

Analysis.-Calculated: Cl, 7.50; N, 5.90; S, 20.30; P, 6.60. Found: Cl, 8.03; N, 5.77; S, 20.31; P, 6.83.

The following is a table of the compounds prepared according to the aforedescribed procedures. Compound numbers have been assigned to each compound and are then used for identification throughout the balance of the application.

TABLE I t? if w RXCNCHZNC CHzSP R R R Compound R X R R Y R R Number CzHs O H H S C H C H O (1.115 0 H H s c n; oiifo phenyl O CH: H S CaHs CzH5O a-naphthyl 0 CH3 H S CzHg CzH5O phenyl 0 CH3 H S OH; CHaO a-naphthyl 0 OH: H: O CzHs C2H50 u-naphthyl 0 CH3 H S CH5 CHaO CzHg 0 CH3 H S CqHs CzH5O CnHs O OH; H S CH3 CHaO C2115 0 OH; H 0 CQHI; CzH5O HC GCH: 0 CH3 H S l-C3H1 i-C3H7O H5 0 02115 H S OIHE :H5O l-C H1 0 OH; H S CzHs CzHsO H; O OH: H S C1H CzH O 01H 0 phenyl H S CzHs C2H5O CgHs 0 CH; CH "-CHCH: S 0 H; 011150 CgHs O C2H5 H S CH3 CHaO C1H5 O phenyl H S CH5 CHzO 2H5 0 H CH3 S CzH5 CzH O CH =CHCH1 0 CH H S C2H5 CzHaO CH3 0 CH3 H S OH; CHaO HC CCH: O CH: H S CH3 CHQO CzHgSCHgCH: 0 CH3 H S CzH5 C2H5O CzHuSCHzCHz O CzH5 H S CzHs CzHgO 01somom 0 0211, H S 0211 canto 26 @somom 0 0211. H S 02115 021150 27 SCHzCHg 0 CzHs H S CzH5 0 1150 28 OHQQS HZCHZ 0 CH3 H s 02.115 0.1150

29 @SCHzCHz 0 CH3 H S CzH5 CzHsO 30 02115501120112 0 02115 H 5 CH CH O 31 o1somom 0 CH3 H s 0211;, 0211.0

32 C2H5SCH2CH2 0 CH H S CH3 CH3() a3 c1somom 0 0211. H s CH 011.0

34 @SCHZCH: 0 02115 H s CH; cmo

35 @samom o 0113 11 s on3 c1130 36 SCHZCHZ O C2115 H S 0113 CI'IQO TABLE I-Continued Compound R X R R Y R' R Number 37 CH3SCH2CH2 on. H s cm omo 38' olsonzcm 0 CH3 H s on. 01130 CH3 S C2H5 H S CzH CzHgO CH S allyl H S C211 C2H O CzH5 S I1-C4H9 H S C2H C2H5O phenyl S 2H5 H S C2H5 CZHflO CH S C2H H S CH CH3O CzHa S CzH H S C2H5 C2H5O CH 0 H CH3 S CzHg C2H5O C2H5 O H C2H5 S C 11 CzH50 Il-C4H9 O H CH3 S 02115 C2H50 i-C4Hfl 0 H C2H5 S 02115 CzHgsO CH 0 H CH3 S CH3 CHaO C2H O H C2H5 S CH CH3O Il-C H9 O H CH3 S CH3 CH3() l-C Ha O H CH S CH CH3O i-C4H O H l-C4H9 S CzHs C2H5O C2H5 O H I1-C4H9 S CzH5 C2H5O C2H5 O H Il-C4Hn S CH3 CHsO CH 0 H H S CH3 CzH C2 5 0 CH H S CH CzHs HC 5 CCHg 0 CH3 H S CH CzHg C2H5 O H l'l-C Ho S CH3 C2H5 isobornyl 0 CH3 H S 0 11 CzH O isobornyl 0 CH H 8 CH3 CH bornyl 0 CH3 H S CzH CzHsO bornyl 0 CH3 H S CH CH O cyclohexyl 0 OH; H S C2H C2H50 011 0 G 0 CH H S C2115 CzHaO 66 N ZQ 0 GHQ 11 s 02H. 021150 C O\ 67 U /NCH2 0 CH3 H S CgH CzHgO C1 0 CH2CH2 0 CH3 H S CzH5 CzH CHgOCHzCHz 0 CH3 H S C2H5 CzH5O n-C4H90CH2CH2 0 CH H S CzH5 C2H50 CzH OCHzCHz 0 CH3 H S C2H5 CzHso CH3 72 CH3O (IJHCHBCHZ 0 CH2 H S 0 H; 0 13 0 73 c1o CHzCHz 0 CH3 H s 02115 021150 N 0. 1 prepared in Example 1. No. 3 prepared in Example 2. No. 16 prepared in Example 3. No. 38 prepared in Example 4. I

As previously mentioned, the herein described novel compositions prepared in the above-described manner are biologically active compounds which are useful and valuable in controlling various insect and acarid species. The compounds of this invention were tested as insecticides and acaricides in the following manner.

vInsecticidal evaluation test.The housefly Musca d0- mestica (Linn) was subjected to evaluation tests for insecticides incorporating the compounds of the present invention.

Twenty-five female flies, three to five days old, were caged in cardboard mailing tubes 3%" in diameter 2%" tall. The cages were supplied with cellophane bottoms and coarse mesh nylon tops. Each cage was provided with food and water. The candidate toxicant was dissolved in a volatile solvent, preferably acetone. The solution was pipetted into a Petri dish bottom, allowed to air dry and placed in a cardboard mailing tube cage. The flies were continuously exposed to the known residue of the active compound in the cage. After twenty-four and forty-eight hours, counts were made to determine living and dead insects. The LD values were calculated using well-known procedures. The results of this insecticidal 55 evaluation test is given in Table II under HP.

The insect species black bean aphidAphis fabae was also employed in the test for insecticidal activity. Young nasturtium plants were used as the host plants for the bean aphid. The host plant was infested with approximately 50 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD value was achieved. These results are given in Table II under the column BA.

Acaricidal evaluation test.The two-spotted mite, Tetranychus telarius (Linn), was employed in tests for miticides. Young pinto bean plants in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with several hundred mites. Dispersions of candidate materials were prepared by dissolving 0.1 gram in 10 ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing 0.0175% v./v. Sponto 221, an emulsifying agent, the amount of water being sufficient to give concentrations of active ingredient ranging from 0.25% to 0.0008%. The test suspensions were then sprayed on the infested pinto bean plants. After seven days, mortalities of post-embryonic and ovicidal forms were determined. The percentage of kill was determined by com- The percentage of kill of each test species was determined by comparison with control plants placed in distilled water or untreated soil. The LD values were calculated. These systemic test results are reported in Table II under the columns SYS for two-spotted mite systemic activity and BAS for the bean aphid systemic activity.

10 p.p.m.

parison with control plants which had not been sprayed with the candidate compounds. The LD value was calculated using well-known procedures. These values are reported under the columns PE and Eggs in Table II.

Systemic evaluation test.-This test evaluates the root absorption and upward translocation of the candidate systemic compound. The two-spotted mite, Tetranychus telarius (Linn.) and the bean aphid, Aphis fabae, were employed in the test for systemic activity.

Young pinto bean plants in the primary leaf stage were used as host plants for the two-spotted mite. The pinto bean plants were placed in bottles containing 200 ml. of the test solution and held in place with cotton plugs. Only the roots were immersed. The test solutions were prepared by dissolvin the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1 percent. The toxicants were initially tested at a concentration of 10 parts per million (p.p.m.). Immediately after the host plant was placed in the test solution it was infested with the test species. Mortalities were determined after seven days.

Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted into one pound of soil that had been treated with the candidate compound. Immediately after planting in the treated soil the plants were infested with the aphids. Concentrations of toxicant in the soil ranged from 10 p.p.m. per pound of soil downward until an LD value was obtained. Mortality was recorded after 72 hours.

In addition to the above presented data it was found that compounds number 21, 56, 57, 58 and 59 have an LD value of 0.1 percent against spotted milkweed bug-Oncopeltus fasciatus (Dallas)and compounds 19 and 45 have an LD of 0.005 percent against spotted milkweed bug. Salt-marsh caterpiller was effectively controlled at a concentration of 0.1 percent by compound number 10. Compound number 56 has an LD of 0.1

percent against German cockroach-Blatella germanica (Linn).

From these data it can be seen that the compounds of the instant application are valuable as insecticides and acaricides. In practice the compounds are usually formulated with an inert adjuvant, utilizing methods wellknown to those skilled in the art, thereby making them suitable 'for application. They may be used in the form of emulsions, non-aqueous solutions, wettable powders, vapors, dusts, dyes and the like, as may be best fitted to the particular utility. The concentration of a compound of the present invention, constituting an effective amount, and the best mode of administration to an insect or acarid pest or its habitat may be easily determined by those skilled in the art of pest control. The disclosure is not meant to limit the action of the compounds to one particular insect or acarid species or mode of effect thereon.

Various changes and modifications may be made without departing from the spirit and scope of the invention described herein as will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the appended claims:

We claim:

1. A compound of the formula wherein X and Y are selected from the group consisting of oxygen and sulfur;

wherein R is a member selected from the group consisting of lower alkyl, lower =alkenyl, lower alkynyl, na-phthyl, phenyl, substituted phenyl, whereinsaid substituents are selected from the group consisting of lower alkoxy, and nitro; bornyl, isobornyl, cyclohexyl, lower alkoxyalkyl, N-phthalimidomethyl 'and S-substituted-thioethyl wherein said substituents are selected from the group consisting of lower alkyl, phenyl, naphthyl, chlorophenyl and methylphenyl; wherein R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl, lower alkenyl and lower alkynyl; wherein R is lower alkyl and R is lower alkoxy or lower alkyl.

2. The compound, N[ethoxycarbamylmethyl] -N-methyl-0,0-diethylphosph0rodithioyl acetamide.

3. The compound, N [methoxy-N'-methylcarbamy1- methyl]-0,0-dimethylphosphorodithioyl acetamide.

4. The compound, N [propargyloxy-N-methylcarbamylmethyl] -0,0-dimethylphosphorodithioyl acetamide.

5. The compound, N[methoxycarbamylmethyl] N- methyl-0,0dimethylphosphorodithioyl acetamide.

6. The compound, N [methoxycarbamylrnethyl]-O- methylethylphosphonodithioyl acetamide.

References Cited UNITED STATES PATENTS 2,864,849 12/ 1958 Schrader .s 260-943 3,022,215 2/1962 Schuler 260-943 XR CHARLES B. PARKER, Primary Examiner.

A. H. SUTTO, Assistant Examiner.

US. Cl. X.R. 

